Well Octopus have now cancelled my duplicate appointment (they booked me for the 27th, and 28th). 
So it should now go ahead on 27th June (in the afternoon). 
In the meantime, OVO screwed up the meter readings they sent Octopus, swapping Night & Day.
I rang Octo support, they took a look and quickly agreed it was a cock-up, and have "raised a dispute" with OVO.
Switching is such fun.